Printing paper, dye-receiving layer forming composition for preparing it, ink composition suitable for it, and image forming method using them

ABSTRACT

Color images with high fixation comparable to that of silver salt photographic images are formed on printing papers, using aqueous ink compositions by ink jet recording. Color images thus formed have high saturation and high resolution. An intercalated compound capable of fixing water-soluble dyes to a printing paper due to the intercalation based on ion-exchanging between them is incorporated into the dye-receiving layer  2  of the paper, on which color images are formed by ink jet recording using an aqueous ink composition containing a water-soluble dye. The content of the intercalated compound in the layer  2  is from 10 to 90% by weight. As the intercalated compound, montmorillonoids are preferred when water-soluble cationic dyes are used while hydrotalcite-group minerals are preferred when water-soluble anionic dyes are used. FIG.  1  is selected.

This is a division of application Ser. No. 08/684,039, filed Jul. 19,1996, which is in turn a division of application Ser. No. 08/271,761,filed Jul. 7, 1994, now U.S. Pat. No. 5,560,996, issued Oct. 1, 1996.

BACKGROUND OF THE INVENTION

The present invention relates to a printing paper capable of forming acolor image with excellent fixability, using an aqueous ink compositioncontaining a water-soluble dye such as a water-soluble cationic dye and,in particular, to a printing paper suitable for ink jet recording. Italso relates to a composition for forming a dye-receiving layer for sucha printing paper, an ink composition suitable for the same, and a methodfor forming an image using them.

As one means for fixing an image information prepared by the use of apersonal computer, etc. on a printing paper in the same manner as insilver salt photography, a method of forming a color image on a printingpaper according to an ink jet recording system using an aqueous inkcomposition is considered hopeful.

In such an ink jet recording system, a liquid, aqueous ink compositioncontaining a water-soluble dye, water, a polyalcohol, etc. is jetted outand adhered onto a printing paper having a dye-receiving layer at thedye-receiving layer through nozzles, using a driving power such aselectric field, heat and pressure to thereby form an image thereon.

The water-soluble dye to be employed in the aqueous ink composition forsuch an ink jet recording system is essentially a water-soluble directdye or acidic dye (hereinafter referred to as “anionic dye”) having asufficient fixability to cellulose constituting paper which isessentially used as a recording medium and capable of yielding a blackcolor by itself. Accordingly, in general, a basic dye (hereinafterreferred to as “cationic dye”) is not used as the dye in an aqueous inkcomposition at present because of its drawbacks that its fixability tocellulose is not sufficient as compared with anionic dyes and that itcannot form a black color if not mixed with others.

On the other hand, the ink-receiving surface of the printing paper to beused in the ink jet recording system using such an aqueous inkcomposition has a dye-receiving layer composed of various additivesdispersed in a water-soluble high polymer having a high affinity fordyes so as to prevent the aqueous ink composition applied thereto frombleeding.

Conventional water-soluble anionic dyes used in the ink jet recordingsystem are, after having been transferred to the dye-receiving layer,captured in the dye-receiving layer due to the interactions such as vander Waals force and hydrogen bonding between them and the constituentcomponents in the dye-receiving layer, according to the theory ofdyeing. Therefore, after formation of images, when other substances suchas solvents or resins having a higher affinity for these dyes arebrought into contact with the formed images or when some heat energyenough to cancel these interactions is applied thereto, then the dyeswill dissolve out or transfer from the dye-receiving layer to such othersubstances whereby the thus-formed images will be blurred without havingcomplete fixation to the layer unlike so-called silver salt photographs.Being different from silver salt photographs, therefore, therefore, theimages formed by the ink jet recording system are problematic in thisrespect.

As some means for solving the problem, it has been proposed tochemically fix such dyes to a dye-receiving layer by forming chemicalbonds between the dyes and the compounds constituting the dye-receivinglayer (see JP-B 62-798, 63-11158, U.S. Pat. No. 4,694,302, JP-A1-225585, etc.—the terms “JP-A” and “JP-B” as referred to herein mean an“examined Japanese patent publication” and an “unexamined Japanesepatent application”, respectively). Concretely, it has been proposed touse reactive dyes as the dye component in the ink composition so as toform covalent bonds between the reactive groups in the reactive dyes andthe active groups in the dye-receiving layer or to form ionic bondsbetween anionic dyes and cationic organic polymers or cationic inorganiclow-molecular compounds in the dye-receiving layer.

However, the conventional means of chemically fixing dyes in thedye-receiving layer by forming chemical bonds therebetween still wereproblematic in that the degrees of reactivity of the dyes and thedye-receiving layer were too high to attain sufficient preservation ofinks and printing papers themselves and also images formed and torealize the fixation of the formed images comparable to that of silversalt photographic images and that, on the contrary, their reactivity wasnot sufficient so that the reaction between them could not be finishedin a short period of time and therefore a long period of time was neededfor forming stable images. In addition, the conventional means had otherproblems that they often needed some auxiliary devices for heating, etc.so as to fix the images, the preparation of dyes for the means was oftendifficult and the usable color hue range was limited. As furtherproblems in these conventional means, the solvent resistance and thelight fastness of the color images formed on printing papers by thesemeans were still unsatisfactory so that the fixation of the imagesthereon was insufficient even though waterproofness was imparted to theimages.

Therefore, in order to make the images formed by the conventional inkjet recording system usable even in the field that needs high imagedurability, for example, including photographs for identity cards andprints for outdoor exhibition, the improvement in the fixation of thecolor images formed is strongly desired along with the improvement intheir saturation and resolution so as to be able to obtain high-qualitycolor images.

Heretofore, particular ink jet recording papers having a dye-receivinglayer formed thereon have been needed as printing papers for ink jetrecording. However, it is strongly desired that any unlimited basematerials having no dye-receiving layer thereon, such as household orofficehold high-quality papers, art papers and ORP sheets, may beapplied to ink jet recording.

SUMMARY OF THE INVENTION

The present invention is to overcome the above-mentioned problems in theprior art, and its object is to form color images having satisfactoryfixation comparable to the fixation of silver salt photographic images,using aqueous ink composition, preferably on printing papers by ink jetrecording with high saturation and high resolution. Specifically, oneobject of the present invention is to form color images havingsatisfactory fixation comparable to the fixation of silver saltphotographic images, on printing papers by ink jet recording with highsaturation and high resolution, even though using aqueous inkcompositions containing water-soluble cationic dyes that have not beenused in the prior art or water-soluble anionic dyes that have heretoforebeen used but could not attain sufficient fixation.

Another object of the present invention is to provide novel means bywhich ink jet recording is possible on any unlimited base materialshaving no dye-receiving layer thereon.

We, the present inventors, having noticed that water-soluble cationicdyes or water-soluble anionic dyes have excellent water-absorbability orwater-swellability and may be firmly fixed to the hydrophilic interlayerin intercalated compounds having cation-exchangeability oranion-exchangeability due to intercalation based on ion-exchangingbetween them, have found that when such an intercalated compound isincorporated into the dye-receiving layer on a printing paper and whenan aqueous ink composition containing water-soluble cationic dyes orwater-soluble anionic dyes is imagewise applied to the dye-receivinglayer, then a color image with excellent fixation and high resolutionmay be formed thereon and that when a colorless, highly-transparentintercalated compound is incorporated into the dye-receiving layer alongwith a binder resin, then the saturation of the color image to be formedmay be improved.

In addition, we have found that when ink jet recording applicable to anyunlimited base materials having no dye-receiving layer is desired, acomposition for forming a dye-receiving layer comprising an intercalatedcompound, a binder resin and a solvent shall be coated over a basematerial just before ink jet recording, preferably by spraying orjetting out the composition over the surface of the base materialthrough the orifices of nozzles, such as spraying nozzles or ink-jettingnozzles. For this purpose, we have found that, in order to stably sprayor jet out the composition for forming a dye-receiving layer through thenozzles, the composition preferably contains a particular solvent andthat the mean particle size of the particles of the intercalatedcompound to be dispersed in the solvent is desired to have a specificvalue or less. On the basis of these findings, we have completed thepresent invention.

Specifically, the present invention provides a printing paper containingan intercalated compound that may fix water-soluble dyes to the paperdue to the intercalation based on ion-exchanging between them.

In addition, the present invention also provides a composition forforming a dye-receiving layer on such a printing paper, which containsan intercalated compound capable of fixing water-soluble dyes to thelayer due to the intercalation based on ion-exchanging between thecompound and dyes, a binder resin and a solvent.

Further, the present invention provides an ink composition applicable tothe above-mentioned printing paper and containing at least water andwater-soluble dye(s), in which said water-soluble dye(s) is/areparticular water-soluble cationic dye(s).

Still further, the present invention provides a method for forming animage on the above-mentioned printing paper, especially that having abase support and a dye-receiving layer, by an ink jet recording systemusing an ink composition containing water-soluble dye(s), in which theabove-mentioned composition for forming a dye-receiving layer is sprayedor jetted out over the base support through nozzles to form adye-receiving layer thereon and thereafter an image is formed on thedye-receiving layer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view showing one embodiment of the printingpaper of the present invention.

FIG. 2 is a cross-sectional view showing another embodiment of theprinting paper of the present invention.

FIG. 3 is a cross-sectional view showing still another embodiment of theprinting paper of the present invention.

In FIGS. 1, 2 and 3; 1 is a base support, 2 is a dye-receiving layer,and 3 is an adhesive layer.

FIG. 4 is a systematic view showing a serial-type ink jet recordingdevice employable in the present invention.

FIG. 5 is a cross-sectional view showing the area of heads in therecording device of FIG. 4.

FIG. 6 is an explanatory view showing the arrangement of nozzles in therecording device of FIG. 4.

FIG. 7(a) to FIG. 7(c) show explanatory views explaining the theory offixation of ink, according to the present invention. Precisely, FIG.7(a) is an explanatory view showing the condition of intercalatedcompounds; FIG. 7(b) is an explanatory view showing the condition ofintercalated compounds where a part of exchangeable cations have beensubstituted by organic cations; and FIG. 7(c) is an explanatory viewshowing the condition of intercalated compounds where water-solublecationic dye molecules have been held between the compounds.

FIG. 8(a) to FIG. 8(c) show explanatory views explaining the theory offixation of ink, according to the present invention. Precisely, FIG.8(a) is an explanatory view showing the condition of intercalatedcompounds; FIG. 8(b) is an explanatory view showing the condition ofintercalated compounds where a part of exchangeable anions have beensubstituted by organic anions; and FIG. 8(c) is an explanatory viewshowing the condition of intercalated compounds where water-solubleanionic dye molecules have been held between the compounds.

DETAILED DESCRIPTION OF THE INVENTION

The printing paper of the present invention will be described in detail,with reference to the drawings.

FIG. 1 to 3 are cross-sectional views showing preferred embodiments ofthe printing paper of the present invention. The embodiment of FIG. 1 iscomposed of a base support 1 and a dye-receiving layer 2 formed thereon;and that of FIG. 2 has an adhesive layer between the dye-receiving layer2 and the base support 1. In the embodiment of FIG. 3, the dye-receivinglayer itself acts also as a base support.

In the present invention, the dye-receiving layer 2 contains anintercalated compound capable of fixing and holding water-soluble dyemolecules by intercalation based on ion-exchanging between them. Forexample, in the embodiments of FIG. 1 and FIG. 2, the structure of thedye-receiving layer 2 may be such that particles of an intercalatedcompound have been uniformly dispersed in a binder resin. In theembodiment of FIG. 3, the dye-receiving layer 2 may be in the form ofpaper to be made from a paper stock mixture containing a beaten pulp, anintercalated compound, a sizing agent, etc. to have such a structurethat the particles of the intercalated compound have been held betweenpulp fibers of the paper. In place of pulp, also usable are syntheticfibers in this embodiment.

As the intercalated compound to be in the dye-receiving layer 2,preferably exemplified are layered inorganic polymers having a layeredstructure and having exchangeable ions capable of being ion-exchangeablefor water-soluble dye molecules in the interlayer between thehydrophilic layers of the compound. Such exchangeable ions of layeredinorganic polymers are exchangeable cations such as sodium ion forwater-soluble cationic dyes, while they and are exchangeable anions suchas carboxyl anion for water-soluble anionic dyes.

As layered inorganic polymers having exchangeable cations (hereinafterreferred to as “cation-exchangeable intercalated compounds”), typicallymentioned are natural or synthetic layered silicates and their sinteredproducts. Of these, typically and preferably used are montmorillonoidsof the following formula (1) having a 3-octagonal smectite structure.These are a kind of clay minerals.

(X,Y)_(2˜3)Z₄O₁₀(OH)₂.mH₂O.(W_(⅓))   (1)

wherein

X represents Al, Fe(III), Mn(III) or Co(III);

Y represents Mg, Fe(II), Ni, Zn or Li;

Z represents Si or Al;

W represents K, Na or Ca;

H₂O is an intercalated water; and

m represents an integer.

Specifically exemplified are natural or synthetic substances such asmontmorillonite, magnesian montmorillonite, iron montmorillonite, ironmagnesian montmorillonite, beidellite, aluminian beidellite, nontronite,aluminian nontronite, saponite, aluminian saponite, hectorite andsauconite, depending on the combination of X and Y and the number oftheir substitutions. In addition, derivatives obtainable from those offormula (1) by substituting the OH group(s) therein by fluorine(s) mayalso be usable in the present invention.

In the present invention, mica-group minerals such as sodium silicicmica, sodium taeniolite and lithium taeniolite are also usable ascation-exchangeable intercalated compounds, in addition tomontmorillonoids of formula (1).

There are known acidic salts such as zirconium phosphate, as well aslayered titanium oxide hydrate, etc., as inorganic polymers orcation-exchangeable intercalated compounds having a layered structureand having exchangeable cations, like synthetic clay minerals. These maybe incorporated into dye-receiving layers that are not needed to betransparent, glossy and white, as having optical light-shieldability orhave intrinsic colors.

In addition to the above-mentioned cation-exchangeable intercalatedcompounds, mentioned are amorphous synthetic silica, etc. as syntheticsilicates having high affinity for cationic dyes. However, these areinferior to montmorillonoids with respect to their dye-fixability ortheir ion-exchangeability in media having a high dielectric constantsuch as water. Therefore, these may be employed when highion-exchangeability is not needed.

When a fine powder having a pure white color, such as a powderysynthetic silicate containing no impurity, is used as thecation-exchangeable intercalated compound mentioned above, it ispossible to form a dye-receiving layer capable of realizing a highsaturation comparable to the saturation of silver salt photographs sincecrystals of the fine powder themselves are optically transparent.

As exchangeable cations to be present between the cation-exchangeableintercalated compound molecules to be used in the present invention,mentioned are inorganic cations that may easily solvate with mediahaving a high dielectric constant, such as water and alcohols, forexample, alkali metal ions such as Li⁺, Na⁺ and K⁺; alkaline earth metalions such as Mg²⁺; H⁺ (in this case, so-called clay acids are refereedto), etc. Of alkaline earth metal ions, Ca²⁺ and Ba²⁺ often givehardly-solvatable interlayers, as compared with the other inorganic ionsmentioned above.

In order to improve the dispersibility of the intercalated compounds inbinder resins which will be mentioned hereinafter and to improve theswellability thereof in non-aqueous solvents such as alcohols, a part ofthe exchangeable inorganic cations in the cation-exchangeableintercalated compounds may be substituted by organic cations capable ofrealizing an effect of broadening the interlayer distance betweenintercalated compound molecules (pillar effect) or an effect ofpartially hydrophobicating the interlayer between them. As such organiccations, preferably usable are quaternary ammonium ions and phosphoniumions, such as alkylphosphonium ions and arylphosphonium ions. Inquaternary ammonium ions to be used in this case, it is preferred thatthree of their four alkyl groups each have 4 or more, preferably 8 ormore carbon atoms. If the number of long-chain alkyl groups is small inthem, their pillar effect is not sufficient so that it becomes difficultto ensure the interlayer distance for the fixing sites (=exchangeableinorganic cations). For instance, when n-octyltrimethylammonium ions areemployed, the interlayer distance cannot be increased to more than about4 angstroms even though they occupy almost all the fixing sites, and, inaddition, they give too much hydrophobicated interlayers and aretherefore unfavorable for the present invention.

As layered inorganic polymers having exchangeable anions (hereinafterreferred to “anion-exchangeable layered compounds”) to be used in thepresent invention, preferably exemplified are layered hydrotalcite-groupminerals composed of AlO₆ octagonal sheets. These are a kind of 0:1 typeclay minerals. As one typical example of such hydrotalcite-groupminerals, mentioned is natural hydrotalcite of a formula (2):

Mg₆Al₂(OH)₁₆.CO₃.4H₂O   (2)

Synthetic hydrotalcites are available as commercial products, thoughhaving compositions somewhat different from that of the naturalhydrotalcite of formula (2). A fine powder of such synthetichydrotalcites does not contain impurities and has a pure white color,and the crystals themselves of the powder is optically transparent.Therefore, when the fine powder is used, it is possible to form adye-receiving layer capable of realizing a high saturation comparable tothat of silver salt photographs.

There are known oxide hydrates and hydroxylated phosphates such as thoseof titanium, zirconium, lanthanum or bismuth, as anion-exchangeableintercalated compounds, in addition to the above-mentionedhydrotalcite-group minerals. These may be incorporated intodye-receiving layers that are not needed to be transparent, glossy andwhite, as having optical light-shieldability or have intrinsic colors.

As exchangeable anions to be present between the anion-exchangeableintercalated compound molecules to be used in the present invention,mentioned are inorganic anions that may easily solvate with media havinga high dielectric constant, such as water and alcohols, for example, NO₃⁻, SO₄ ²⁻, ClO₄ ⁻, Fe(CN)₆ ⁴⁻, heteropolyphophato ions, hydrophilicorganic anions such as lower carboxylato ions, etc. Higher carboxylatoions often give hardly-solvatable interlayers, as compared with theabove-mentioned anions.

In order to improve the dispersibility of the intercalated compounds inbinder resins which will be mentioned hereinafter and to improve theswellability thereof in non-aqueous solvents such as alcohols, a part ofthe exchangeable anions in the anion-exchangeable intercalated compoundsmay be substituted by organic anions capable of realizing an effect ofbroadening the interlayer distance between intercalated compoundmolecules (pillar effect) or an effect of partially hydrophobicating theinterlayer between them. As such organic anions, for example, mentionedare carboxylato anions, sulfonato anions, ester anions, phosphate esteranions, etc.

In general, such anions have alkyl group(s) or alkenyl group(s). If thenumber of carbon atoms in such groups is small, the pillar effect of thecompounds is not sufficient so that it becomes difficult to ensure theinterlayer distance for the fixing sites (=exchangeable inorganicanions). If, however, it is too large, the substitution by the anions isdifficult. For these reasons, the number of carbon atoms in such groupsis preferably from 5 to 20.

In the printing paper of the present invention, the above-mentionedintercalated compound (cation-exchangeable intercalated compound oranion-exchangeable intercalated compound) is dispersed and held in abinder resin. As the binder resin, usable are ordinary thermoplasticresins. Preferred are hydrophilic resins in which intercalated compoundsare easily dispersible and into which solvents in aqueous inkcompositions, such as water and alcohols, may penetrate. As such binderresins, preferably exemplified are polyvinyl butyral resins,hydroxypropyl cellulose resins, vinyl pyrrolidone-vinyl acetatecopolymer resins, polyvinyl alcohol resins, polyvinyl acetal resins,etc. It is preferred that these binder resins do not substantially havesubstituents that retard the dye-fixability of intercalated compounds,for example groups, such as ammonium groups, that may be more easilyion-exchanged and held in the interlayer of intercalated compoundsrelatively than water-soluble dyes and groups that will promote theaggregation of intercalated compounds.

Where such hydrophilic resins or water-soluble resins are used as thebinder resin, it is preferred that they are crosslinked with urethanecrosslinking agents, etc., so as to ensure the waterproofness of thefilm after formation of images thereon. Therefore, the binder resins foruse in the present invention preferably have substituents capable ofparticipating in the crosslinking reaction, such as OH group andcarboxyl group, in such a degree that the substituents do not retard thedye-fixability of intercalated compounds.

Regarding the content of the intercalated compound to be in thedye-receiving layer 2, if it is too small, the dye-fixing effect of thelayer will be insufficient. If, however, it is too large, the content ofthe binder resin in the layer will be relatively small so that thesoftness of the dye-receiving layer 2 will be lowered. For thesereasons, the content is preferably from 10 to 90% by weight, morepreferably from 40 to 80% by weight, of the dye-receiving layer 2(calculated in terms of the solid content in the layer).

If the content of the binder resin in the dye-receiving layer 2 is toosmall, the dye-receiving layer 2 will be hard so that its filmingproperty will be worsened. If, on the other hand, it is too large, thecontent of the intercalated compound in the layer will be relativelysmall to lower the dye-fixability of the layer. For these reasons, thecontent is preferably from 2 to 50% by weight, more preferably from 5 to20% by weight, of the dye-receiving layer 2 (calculated in terms of thesolid content in the layer).

A plasticizer for controlling the glass transition point Tg of binderpolymers may be added to the dye-receiving layer 2, provided that itdoes not retard the dye-fixability of the intercalated compound in thelayer. In addition, various additives, for example, a water-repellentfor controlling water-repellency, an ultraviolet absorbent for improvinglight fastness, a brightening agent for improving image quality, etc.may be added to the layer 2.

The base support 1 to be used in the embodiments of FIG. 1 and FIG. 2 ofthe present invention may be freely chosen from among paper, syntheticpapers, plastic papers, metal sheets, metal foils, aluminium-coatedplastic films, etc. When used for OHP or the like, the base support 1must be light-permeable.

For the adhesive layer 3 to be in the embodiment of FIG. 2, usable areany adhesives that have heretofore been employed in the field of videos,printing papers, etc. For instance, polyurethane adhesives are used.

In the printing paper of the embodiment of FIG. 3, intercalatedcompounds are held between fibers of pulp, etc. that constitute paper,as so mentioned hereinabove. In this case, the content of theintercalated compound in the paper is preferably from 10 to 70% byweight, more preferably from 20 to 50% by weight, relative to the solidcontent in the paper, in consideration of the dye-fixability of thecompound and the quality of the paper.

The printing paper of the present invention may be prepared by knownmethods.

For example, the printing paper of the embodiment of FIG. 1 is preparedas follows: An intercalated and a binder resin are dispersed in a mediumhaving a high dielectric constant, and the resulting dispersion iscoated over the base support 1 by known coating means, for example, bydoctor blading, and then dried to form the dye-receiving layer 2. Forinstance, a composition for forming a dye-receiving layer is prepared,and the composition is coated over the base support 1 by known coatingmeans and dried to form the dye-receiving layer 2. Next, a release sheetsuch as a lubricant-treated polyethylene terephthalate film issuperposed over the dye-receiving layer 2 and attached thereto underheat and pressure whereby the dye-receiving layer 2 is firmly adhered tothe base support 1. Then, the polyethylene terephthalate film is peeledoff from the layer 2 to finally obtain the printing paper of FIG. 1.Alternatively, the composition for forming a dye-receiving layer may besprayed or jetted out over the base support 1 through spraying nozzlesor ink-jetting nozzles and then dried to form the dye-receiving layer 2thereon to obtain the printing paper.

The printing paper of the embodiment of FIG. 2 is prepared as follows:First, a dispersion obtained by dispersing an intercalated compound anda binder resin optionally along with other additives such as acrosslinking agent in a medium having a high dielectric constant isapplied to a lubricant-treated polyethylene film by known coating means,for example, by doctor blading, and then dried to form the dye-receivinglayer 2 thereon. Apart from this, an adhesive composition is coated on aseparate base sheet to form an adhesive layer thereon. The two wereattached to each other in such a way that the adhesive layer faces thedye-receiving layer, and heated under pressure to prepare the printingpaper of FIG. 2 where the dye-receiving layer 2 has been laminated onthe base support 1 via the adhesive layer 3. For instance, a compositionfor forming a dye-receiving layer is applied to a base support such as alubricant-treated polyethylene film by known coating means, for example,by doctor blading, and then dried to form a dye-receiving layer transfersheet (not shown) having a dye-receiving layer thereon. Apart from this,an adhesive composition is coated on a separate base support to form anadhesive layer thereon. The two were attached to each other in such away that the adhesive layer of the latter faces the dye-receiving layerof the former and heated under pressure to prepare the printing paper ofFIG. 2 where the dye-receiving layer 2 has been laminated on the basesupport 1 via the adhesive layer 3.

The printing paper of the embodiment of FIG. 3 is prepared as follows: Abeaten pulp and an intercalated compound are suspended in wateroptionally along with additives such as a sizing agent, and theresulting suspension is sheeted and dewatered by paper-making to obtainthe printing paper of FIG. 3.

The composition for forming a dye-receiving layer of the presentinvention, which is used in preparing the printing paper of FIG. 1 orFIG. 2, will be mentioned below.

The composition for forming a dye-receiving layer of the presentinvention contains an intercalated compound capable of fixing andholding water-soluble dyes due to intercalation based on ion-exchangingbetween them, a binder resin and a solvent, and optionally additivessuch as a crosslinking agent. Since the composition for forming adye-receiving layer contains an intercalated compound capable of firmlyfixing water-soluble dyes therewith, it is preferably used for forming adye-receiving layer on a printing paper for ink jet recording which usesan aqueous ink composition. The intercalated compounds and the binderresins to be used in preparing the composition for forming adye-receiving layer may be the same as those to be used in preparing theprinting paper of the present invention.

Specifically, as the intercalated compounds to be in the composition forforming a dye-forming layer of the present invention, usable are layeredinorganic polymers having exchangeable cations or exchangeable anions.As layered inorganic polymers having exchangeable cations, preferred aremontmorillonoids such as typically those of the above-mentioned formula(1). As layered inorganic polymers having exchangeable anions, preferredare hydrotalcite-group minerals such as typically the compound of theabove-mentioned formula (2).

As the binder resins to be in the composition for forming a dye-forminglayer of the present invention, preferably used are hydrophilic resinssuch as typically polyvinyl butyral resins, hydroxypropyl celluloseresins, vinyl pyrrolidone-vinyl acetate copolymer resins, polyvinylalcohol resins, polyvinyl acetal resins, etc.

The size of the particles of the intercalated compound to be in thecomposition for forming a dye-receiving layer is not specificallydefined, provided that they may be stably dispersed in the composition.When the composition is sprayed or jetted out through nozzles to formthe intended dye-receiving layer, for example, in the manner mentionedabove, it is preferred that the particles have a mean particle size of 1μm or less, preferably from 0.01 to 0.5 μm, in order to prevent thenozzles from clogging and to ensure the high dispersion stability of thecomposition.

As the solvent to be in the composition for forming a dye-receivinglayer, preferred are solvents having a high dielectric constant so as toensure the dispersion of the composition. As such solvents, for example,mentioned are lower alcohols such as isopropanol and ethanol.

The proportions of the constituent components in the composition forforming a dye-receiving layer are preferably such that the content ofthe intercalated compound is from 10 to 80% by weight, that of thebinder resin is 50% by weight or less, and that of the solvent is from20 to 60% by weight, in consideration of the dye-fixing property and thefilming property of the composition.

Ink compositions suitable to the printing paper of the present inventionmentioned above, which are suitable for ink jet recording, will bementioned hereunder.

The ink composition of the present invention comprises at least waterand a water-soluble dye that may be fixed and held by the intercalatedcompound in the dye-fixing layer due to intercalation based onion-exchanging between them. Precisely, the ink composition contains atleast water and a water-soluble dye, and the water-soluble dye is fixedand held by the intercalated compound in the dye-receiving layer formedon the printing paper of the present invention due to intercalationbased on ion-exchanging between the compound and the dye. Accordingly,the water-soluble dyes to be used in the present invention arepreferably those that may easily penetrate into the interlayers in theintercalated compounds. As such dyes, for example, preferably used arewater-soluble cationic dyes having an anion-countering property andhaving a partition coefficient in a water/chloroform (1/1, by weight)system of 0.1 or more.

Water-soluble dyes usable in the present invention include water-solublecationic dyes (water-soluble basic dyes) and water-soluble anionic dyes(water-soluble direct dyes and water-soluble acidic dyes).

As water-soluble cationic dyes, usable in the present invention are azodyes, triphenylmethane dyes, azine dyes, oxazine dyes, thiazine dyes andthe like having amine salts residues or quaternary ammonium groups. Asspecific examples of these, mentioned are C.I. Basic Yellows 1, 2, 11,13, 14, 19, 21, 25, 28, 32, 33, 34, 35 and 36, for yellow dyes; C.I.Basic Reds 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 38,39 and 40, and C.I. Basic Violets 7, 10, 15, 21, 25, 26, 27 and 28, formagenta dyes; C.I. Basic Blues 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26,28, 29, 40, 41, 44, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68 and 75,for cyan dyes; and C.I. Basic Blacks 2 and 8, for black dyes. Especiallypreferred are C.I. Basic Yellows 21, 36, 67 and 73, and water-solublecationic dyes of the following formulae (3), (4), (5), (6), (7), (8),(9) and (10):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹²independently represent a hydrogen atom, a halogen atom, a cyano group,an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, anaryloxy group, an aralkyl group, an aralkoxy group, an alkenyl group, analkenoxy group, an alkoxycarbonyl group, an acyloxy group or an acylgroup, which may optionally be substituted;

R¹ and R²; R³ and R⁴, R⁷ and R⁸; R⁹ and R¹⁰; R¹⁰ and R¹¹; and R¹¹ andR¹² may be bonded to each other to form a ring; and

Z⁻ represents a counter ion.

wherein R¹³, R¹⁴, R¹⁵ and R¹⁶ independently represent a hydrogen atom, ahalogen atom, a cyano group, an alkyl group, a cycloalkyl group, analkoxy group, an aryl group, an aryloxy group, an aralkyl group, anaralkoxy group, an alkenyl group, an alkenoxy group, an alkoxycarbonylgroup, an acyloxy group or an acyl group, which may optionally besubstituted; and

Z⁻ represents a counter ion.

wherein R¹⁷, R¹⁸, R¹⁹, R²⁰ and R²¹ independently represent a hydrogenatom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group,an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, anaralkoxy group, an alkenyl group, an alkenoxy group, an alkoxycarbonylgroup, an acyloxy group or an acyl group, which may optionally besubstituted;

R²⁰ and R²² may be bonded to each other; and

Z⁻ represents a counter ion.

wherein R²², R²³, R²⁴, R²⁵ and R²⁶ independently represent a hydrogenatom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group,an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, anaralkoxy group, an alkenyl group, an alkenoxy group, an alkoxycarbonylgroup, an acyloxy group or an acyl group, which may optionally besubstituted;

R²⁵ and R²⁶ may be bonded to each other; and

Z⁻ represents a counter ion.

wherein R²⁷ represents a substituted or unsubstituted aryl group, or asubstituted or unsubstituted heterocyclic group;

R²⁸ and R²⁹ independently represent a hydrogen atom, a halogen atom, acyano group, an alkyl group, a cycloalkyl group, an alkoxy group, anaryl group, an aryloxy group, an aralkyl group, an aralkoxy group, analkenyl group, an alkenoxy group, an alkoxycarbonyl group, an acyloxygroup, an acyl group or an acylamino group, which may optionally besubstituted;

R³⁰ represents a substituted or unsubstituted alkyl group;

R³¹ and R³² independently represent a hydrogen atom, a substituted orunsubstituted alkyl group, or a substituted or unsubstituted aralkylgroup, or R³¹ and R³² may be bonded to each other; and

Z⁻ represents a counter ion.

wherein R³³, R³⁴, R³⁵ and R³⁶ independently represent a hydrogen atom, ahalogen atom, a cyano group, an alkyl group, a cycloalkyl group, analkoxy group, an aryl group, an aryloxy group, an aralkyl group, anaralkoxy group, an alkenyl group, an alkenoxy group, an alkoxycarbonylgroup, an acyloxy group or an acyl group, which may optionally besubstituted;

R³⁵ and R³⁶ may be bonded to each other; and

Z⁻ represents a counter ion.

wherein R³⁷, R³⁸, R³⁹ and R⁴⁰ independently represent a hydrogen atom, ahalogen atom, a cyano group, an alkyl group, a cycloalkyl group, analkoxy group, an aryl group, an aryloxy group, an aralkyl group, anaralkoxy group, an alkenyl group, an alkenoxy group, an alkoxycarbonylgroup, an acyloxy group or an acyl group, which may optionally besubstituted;

R³⁹ and R⁴⁰ may be bonded to each other; and

Z⁻ represents a counter ion.

These water-soluble cationic dyes generally have an inorganic anion asthe counter ion, and many of them exist as salts of strong acids.Therefore, since their aqueous solutions are generally acidic, it isdesired to neutralize them with basic salts in order to prevent metalparts that are kept in contact with ink compositions containing suchwater-soluble cationic dyes from being corroded by them. For example, itis preferred to treat the counter ions of inorganic anions with sodiumsalts, etc. of organic anions such as carboxylato ions to therebysubstitute the organic anions for the former. In this case, it isdesired not to make the salts of dyes thus formed with such organicanions too highly hydrophobic or not to reduce the affinity between thesalts of dyes with such organic acids and intercalated compounds, inorder not to reduce the affinity of intercalated compounds forwater-soluble cationic dyes.

Of water-soluble dyes for use in the present invention, water-solubleanionic dyes have a monoazo group, a disazo group, an anthraquinoneskeleton, a triphenylmethane skeleton or the like as the chromophoricgroup and additionally have from 1 to 3 anionic water-soluble groupssuch as sulfonato groups or carboxylic groups in one molecule. Aspreferred examples of such water-soluble anionic dyes for use in thepresent invention, mentioned are C.I. Direct Yellows 1, 8, 11, 12, 24,26, 27, 28, 33, 39, 44, 50, 58, 85, 86, 87, 88, 89, 98, 100 and 110, foryellow direct dyes; C.I. Direct Reds 1, 2, 9, 11, 13, 17, 20, 23, 24,28, 31, 33, 37, 39, 44, 46, 62, 63, 75, 79, 80, 81, 83, 84, 89, 95, 99,113, 197, 201, 218, 220, 224, 225, 226, 227, 228, 229, 230 and 321, formagenta direct dyes; C.I. Direct Blues 1, 2, 6, 8, 15, 22, 25, 41, 71,76, 77, 78, 80, 86, 90, 98, 106, 108, 120, 158, 160, 163, 165, 168, 192,193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237,246, 248 and 249, for cyan direct dyes; C.I. Direct Blacks 17, 19, 22,32, 38, 51, 56, 62, 71, 74, 75, 77, 97, 105, 106, 107, 108, 112, 113,117, 118, 132, 133 and 146, for black direct dyes; C.I. Acid Yellows 1,3, 7, 11, 17, 19, 23, 25, 29, 36, 38, 40, 42, 44, 49, 59, 61, 70, 72,75, 76, 78, 79, 98, 99, 110, 111, 112, 114, 116, 118, 119, 127, 128,131, 135, 141, 142, 161, 162, 163, 164 and 165, for yellow acidic dyes;C.I. Acid Reds 1, 6, 8, 9, 13, 14, 18, 26, 27, 32, 35, 37, 42, 51, 57,75, 77, 80, 82, 83, 85, 87, 88, 89, 92, 94, 97, 106, 111, 114, 115, 117,118, 119, 129, 130, 131, 133, 134, 138, 143, 145, 154, 155, 158, 168,180, 183, 184, 186, 194, 198, 199, 209, 211, 215, 216, 217, 219, 249,252, 254, 256, 257, 262, 265, 266, 274, 276, 282, 283, 303, 317, 318,320, 321 and 322, for magenta acidic dyes; C.I. Acid Blues 1, 7, 9, 15,22, 23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 72, 74, 78, 80, 82,83, 90, 92, 93, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129,130, 131, 138, 140, 142, 143, 151, 154, 158, 161, 166, 167, 168, 170,171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 229, 234 and 236for cyan acidic dyes; C.I. Acid Blacks 1, 2, 7, 24, 26, 29, 31, 44, 48,50, 51, 52, 58, 60, 62, 63, 64, 67, 72, 76, 77, 94, 107, 108, 109, 110,112, 115, 118, 119, 121, 122, 131, 132, 139, 140, 155, 156, 157, 158,159 and 191, for black acidic dyes.

These water-soluble anionic dyes may directly be incorporated into inkcompositions as they are. If desired, however, a part of the countercations of these dyes may be substituted by organic cations such asonium ions, so as to improve the compatibility of the dyes with alcoholswhich are in ink compositions as auxiliary components and to prevent thedyes from bleeding in the dye-receiving layer on the printing paper. Inthis case, it is desired not to make the salts of dyes thus formed withsuch organic cations too highly hydrophobic, in order not to reduce theaffinity of intercalated compounds for water-soluble anionic dyes.

The ink composition of the present invention may contain, if desired,additives that have heretofore been incorporated into conventionalaqueous ink compositions for ink jet recording, such as anti-fungalagents, etc., in addition to the above-mentioned water-soluble cationicdyes or water-soluble anionic dyes.

Where images are formed, using the printing paper of the presentinvention such as those shown in FIGS. 1 to 3 and the above-mentionedink composition, for example, the ink composition may be jetted outthrough an ordinary ink jet recording device equipped withbubble-driving jet nozzles, piezo-driving jet nozzles or the like,selectively onto the dye-receiving layer on the printing paper of thepresent invention in accordance with the image signal applied to thedevice.

Where the composition for forming a dye-receiving layer of the presentinvention is desired to be sprayed or jetted out onto a base supportthrough spraying nozzles or ink-jetting nozzles and dried to form adye-receiving layer thereon to obtain a printing paper, an ink jetprinter equipped with nozzles through which the composition for forminga dye-receiving layer is sprayed or jetted out onto the base support isemployed. Using the ink jet printer, a dye-receiving layer may be formedon the base support simultaneously with forming an image on the layer,by ink jet recording. According to the image forming methodcharacterized in that the dye-receiving layer is formed on the basesupport just before forming an image thereon by ink jet recording,particular commercial papers for exclusive use in ink jet recording arenot needed but any ordinary printing materials such as household orofficehold high-quality papers or OHP sheets may be used for formingcolor images thereon by ink jet recording. The image forming method iswithin the scope of the present invention.

One example of a printer to be used for the image forming method will beshown in FIG. 4. Precisely, FIG. 4 is a systematic view showing aso-called serial-type ink jet recording device, which is additionallyequipped with a means for forming a dye-receiving layer. The means isprovided with nozzles through which the composition for forming adye-receiving layer of the present invention is jetted out onto a basesupport to form a dye-receiving layer thereon. FIG. 5 is an explanatoryview showing the cross section of the part around the heads of therecording device of FIG. 4; and FIG. 6 is an explanatory view showingthe arrangement of nozzles in the heads.

Using the serial-type ink jet recording device of this kind, printing iseffected in such a way that the printing head 41 equipped with inknozzles through which an ink is jetted out is scanned by reciprocatingmotion in the widthwise direction (arrowed by “x”) of the recordingmedium 42 such as paper, plastic film, cloth, etc. while the recordingmedium 42 is conveyed in the direction arrowed by “y”, as shown in FIG.4 and FIG. 5.

In this embodiment, the printing head 41 is held by the shaft 43, whilebeing scanned by the belt 45 wound around the head-feeding motor 44. Asthe printing head 41, for example, usable is such that it obtains anink-jetting pressure by the deformation of a so-called piezo-device orsuch that it obtains the same by boiling an ink with a heating device.The printing head 41 has plural ink nozzles 46 arranged in the mannershown in FIG. 6. Though the printing head generally has plural inknozzles such as those shown in this embodiment, but it may have only oneink nozzle.

The recording medium 42 is conveyed by the paper-feeding rollers 48 thatare rotated by the paper-feeding motor 47.

The serial-type ink jet recording device of this embodiment is equippedwith the jetting head 50 having the jet nozzles 49 for jetting out thecomposition for forming a dye-receiving layer, in the scanning directionof the printing head 41 (see FIG. 6). The jet nozzles 49 are disposed inthe positions corresponding to the ink nozzles 46 for jetting out an inktherethrough, in such a way that each of the former corresponds to eachof the latter by one to one.

On the side opposite to the jetting head 50, the printing head 41 andthe recording medium 42, provided is the heater 51 composed of the lamp51 a and the reflective sheet 51 b, as the means for drying thecomposition for forming a dye-receiving layer that has been jetted outfrom the jetting head 51 and the ink that has been jetted out from theprinting head 41. However, the drying means of this type is not alwaysnecessary in this embodiment but may optionally be provided therein whenthe drying speed of the jetted composition for forming a dye-receivinglayer or that of the jetted ink is low if not forcedly dried. Regardingthe position of the drying means, if provided, the heater 51 ispositioned just below the printing head 41 in FIG. 5, but this is notlimited to the illustrated one.

The recording device having the illustrated structure (FIG. 4) may bepreferably applied to the image forming method of the present invention,when the ink composition of the invention and the composition forforming a dye-receiving layer of the invention are combined and set inthis.

Referring to a synthetic saponite to be included in montmorillonoids, asone example of the intercalated compounds to be in the dye-receivinglayer of the printing paper of the present invention which is suitableto ink jet recording with an aqueous ink composition, the compound has alayered structure composed of the repetition of three-layered structureshaving normal octahedrons as the base skeleton, in which the layers 70hold interlayer water and sodium ions 70 therebetween (see FIG. 7(a)).In this, the interlayer distance is referred to as d1.

So as to improve the dispersibility of a binder resin in theintercalated compound and to improve the swellability of the compoundwith non-aqueous media such as alcohols, the synthetic saponite 70 isswollen with water and organic cations such as quaternary ammonium ions72 are added thereto, as shown in FIG. 7(b). This results inion-exchanging, by which quaternary ammonium ions 72 are capturedbetween the layers in place of sodium ions 71. The interlayer distanced2 in this condition is larger than the interlayer distance d1 in thenon-treated synthetic saponite.

When the ink composition of the present invention is applied to thedye-receiving layer on the printing paper having therein the syntheticsaponite shown in FIG. 7(a) or FIG. 7(b) or its sintered product, thewater-soluble cationic dye molecules to be contained in the inkcomposition are rapidly transferred into the interlayers in theintercalated compound in the dye-receiving layer along with a solvent(e.g., a liquid having a high dielectric constant, such as water,alcohols), while causing ion-exchanging between the dye cations and thesodium ions 71 or the quaternary ammonium ions 72 existing in theinterlayers whereby the water-soluble cationic dye molecules 73 arecaptured in the interlayers in the synthetic saponite 70, as shown inFIG. 7(c).

The water-soluble cationic dye molecules 73 that have been captured inthe interlayers in the synthetic saponite 70 form ionic bonds to thesynthetic saponite 70 and are thereby firmly fixed to the dye-receivinglayer. Accordingly, using the printing paper and the ink composition ofthe present invention, color images with high fixation comparable tothat of silver salt photographic images may be formed with highresolution. Where transparent intercalated compounds and binder resinsare used in this case, color images with high saturation may be formed.

The following is another embodiment where a synthetic hydrotalcite of ananion-exchangeable intercalated compound is used in place of thesynthetic saponite of a cation-exchangeable intercalated compound.

The illustrated hydrotalcite has exchangeable anions such as carbonatoions 81 in its interlayers and on the edges of the octahedronsconstituting the layers 80. The interlayer distance in this condition isreferred to as d1 (FIG. 8(a)).

When the synthetic hydrotalcite 80 is swollen with water and organicanions such as higher fatty acid ions 82 are added thereto, then thesecause ion-exchanging as shown in FIG. 8(b) with the result that thesefatty acid ions 82 are captured in the interlayers in place of thecarbonato ions 81 and function as interlayer pillars. Under thiscondition, the interlayer distance d2 is larger than the interlayerdistance d1 in the non-treated synthetic hydrotalcite. However, thesubstitution by these organic anions must not be effected tooexcessively, in order not to kill all the fixing sites in the dyemolecules or not to reduce the water-absorbing capacity of the dye to animpractical degree.

Since the thus ion-exchanged synthetic hydrotalcite holds the fatty acidions 82 having hydrophobic chains in its interlayers, its swellabilitywith non-aqueous media such as alcohols is increased higher than that ofthe non-treated one.

When ink drops containing direct dyes or acidic dyes are jetted out ontoa printing paper having thereon a dye-receiving layer formed by coatinga dispersion of the synthetic hydrotalcite having the interlayerdistance of d1 or d2 or its sintered product dispersed in athermoplastic resin, on a base support followed by drying it thereon, toform an image on the paper, the water-soluble anionic dyes (direct dyesor acidic dyes) contained in the ink composition are immediatelytransferred into the interlayers in the intercalated compound containedin the dye-receiving layer along with the solvent (liquid having a highdielectric constant such as water, alcohols) to cause ion-exchangingbetween the dye anions and the carbonato ions 81 or, as the case may be,the fatty acid ions 82 on the surfaces of the interlayers, by which thewater-soluble anionic dye molecules 83 are captured in the interlayersin the synthetic hydrotalcite 80, as shown in FIG. 8(c).

The water-soluble anionic dye molecules 73 that have been captured inthe interlayers in the synthetic hydrotalcite 80 form ionic bonds to thesynthetic hydrotalcite 80 and are thereby firmly fixed to thedye-receiving layer. This phenomenon is not limited to occur only in theinterlayers but may be expected to occur also in the other surfaceshaving the similar behaviors.

Accordingly, using the printing paper and the ink composition of thepresent invention, color images with high fixation comparable to that ofsilver salt photographic images may be formed with high resolution.Where transparent intercalated compounds and binder resins are used inthis case, color images with high saturation may be formed.

According to the present invention, since the water-soluble dyescaptured in the interlayers in the intercalated compounds are notdirectly exposed to any external light, the images formed may haveextremely improved fastness to light.

The present invention will be explained in more detail with reference tothe following examples, which, however, are not intended to restrict thescope of the present invention. In the following examples, “parts” areby weight.

EXAMPLE 1 Preparation of water-soluble cationic dye-containing aqueousink compositions

The components shown in Table 1 and Table 2 below were uniformly blendedto prepare Group (I) and Group (II) of aqueous ink compositions ofyellow, magenta, cyan and black colors for forming color images.

In preparing the aqueous ink compositions of Group (II), a part of thecounter ions of each dye were substituted by organic anions(paratoluenesulfonato ions) so as to elevate the affinity of the dye fornon-aqueous media to thereby increase the content of the non-aqueousmedium in the composition.

TABLE 1 Group (I) of Aqueous Ink Compositions Component Amount Dye  2parts Yellow C.I. Basic Yellow 2 Magenta C.I. Basic Red 46 Cyan C.I.Basic Blue 3 Black C.I. Basic Black 2 Glycerin  2 parts DiethyleneGlycol  6 parts Water 30 parts

TABLE 2 Group (II) of Aqueous Ink Compositions Component Amount Dye  2parts Yellow C.I. Basic Yellow 51 Magenta C.I. Basic Red 23 Cyan C.I.Basic Blue 75 Black C.I. Basic Black 2 Sodium  1 partParatoluenesulfonate Diethylene Glycol 20 parts Polyethylene Glycol 20parts Water 50 parts

EXAMPLE 2 Preparation of aqueous cationic dye-receiving printing papers

150 g of synthetic hectorite (LAPONITE, trade name—made by Nippon SilicaIndustrial Co.) were put in one kg of ethanol solution containing 10 wt.% of polyvinyl butyral (BL-1, trade name—made by Sekisui ChemicalIndustry Co.) and dispersed with a roll mill for 2 days to obtain asuspension. The suspension was coated on one surface of a 100 μm-thickneutral paper, using a doctor blade, and dried with a hot air at 110° C.for one minute to form a solid film thereon.

Next, a 50 μm-thick polyethylene terephthalate film was covered over thesolid film and heated under pressure for heat-welding, by passing themthrough rollers each having a surface temperature of 120° C. at a speedof one cm/sec. After cooled to room temperature, the uppermostpolyethylene terephthalate film was peeled off to obtain a printingpaper composed of the neutral paper and a transparent and glossy layerformed thereon.

The thus-prepared printing papers were set in a paper-feeding tray in anink jet printer (Desk Jet 505J, trade name—made by Hewlett-Packard,Ltd.) and printed by ink jet recording, using the aqueous inkcompositions of Group (I).

After printing, the printed papers were left as they were for about 5minutes and then subjected to a water-proofness test (fixation test), inwhich their surfaces having images thereon were dipped in water for 24hours to check as to whether or not the dye dissolved out into water. Asa result, no dye dissolved out into water throughout the whole region ofthe printed image ranging from the low-density area to the high-densityarea. Thus, the water-proofness of the printed image was excellent.

COMPARATIVE EXAMPLE 1

Printing papers were prepared in the same manner as in Example 2, exceptthat the synthetic hectorite was not used. These printing papers wereprinted by ink jet recording and then subjected to the water-proofnesstest, in the same manner as in Example 2. As a result, the dye in theprinted images began to dissolve out into water immediately after theprinted papers were dipped in water, and it almost completely dissolvedout into water in several hours. In this comparative example, theprinted images had no fixation.

EXAMPLES 3 TO 6 Preparation of water-soluble cationic dye-receivingprinting papers

100 cc of an aqueous suspension containing 3 g of beaten pulp(RESTIGOUCHE Bleached Pulp HITEE; csf 270 cc) were put in a beakercontaining therein synthetic saponite (SUMECTONSA, trade name—made byKunimine Industrial Co.) of the amount indicated in Table 3 below, andthe same amount of water was added thereto. Then, while these werelightly stirred with a spoon, 0.06 g (12.0% as its solid content) of asizing agent (MACOPELU 12, trade name—made by Dick Hercules Co.) toprevent the paper from shrinking in the presence of water and 0.12 g ofa fixing agent (KAIMEN 557-7, trade name—made by Dick Hercules Co.) toaccelerate pulp-to-pulp adhesion or pulp-to-pigment adhesion were addedthereto. The resulting mixture was ground in a mixer for about 2minutes, then put in a water tank in a paper-making machine, and thedispersion in the tank was stirred with a mesh-like stirrer.

Next, water was drawn out of the water tank all at a time, and awater-absorbing paper was put over the sheet-like substance deposited atthe bottom of the water tank and pressed with a heavy stone roller.Next, the water-absorbing paper was removed, and the raw paper formed atthe bottom of the tank was peeled off from the lowermost screen mesh anddewatered in a drier at 160° C. to

TABLE 3 Amount of Synthetic Saponite Added Example No. Amount Added (g)3 3 4 2 5 1.0 6 0.5

The thus-obtained printing papers were printed by ink jet recording inthe same manner as in Example 2, using the aqueous ink compositions ofGroup (II) having a higher content of the non-aqueous medium than theaqueous ink compositions of Group (I). The penetration of the aqueousink compositions into the printing papers was good.

Next, the thus-printed papers were subjected to a solvent resistancetest (using ethanol), in which the papers were dipped in ethanol tocheck as to whether or not the dye dissolved out into ethanol. As aresult, substantially no dye dissolved out from the printed papers ofExamples 3 to 5 at every density of the printed images, and the printedimages had excellent solvent resistance (fixation). In the printedpapers of Example 6, the dye dissolved out only slightly from thehigh-density area in the formed images, which, however, causes noproblem in practical use. From these results, it is noted that the theformed images, which, however, causes no problems in practical use. Fromthese results, it is noted that the solvent resistance (alcoholresistance) of the printing papers of these examples was greatlyimproved due to the incorporation of the intercalated compoundthereinto.

COMPARATIVE EXAMPLE 2

Printing papers were prepared in the same manner as in Examples 3 to 6,except that the synthetic saponite was not used. These printing paperswere printed by ink jet recording and subjected to the solventresistance test for the printed images, in the same manner as inExamples 3 to 6. As a result, the printed dye immediately dissolved outfrom all the image regions having various densities. Thus, the solventresistance of the printing papers in this comparative example was notgood.

EXAMPLE 7 Preparation of water-soluble cationic dye-receiving printingpapers

20 g of synthetic smectite (SWN, trade name—made by Corp Chemical Co.)were dispersed and swollen in one liter of water, and ethanol of thesame amount was added to the dispersion. While stirring, 0.65 g (1 mgequivalent) of tetra-n-decylammonium bromide dissolved in 200 cc ofethanol were dropwise added to the dispersion. This was allowed to standat room temperature for one day, whereupon granular aggregatesprecipitated. The precipitates were separated from the dispersion byfiltration and washed with ethanol to remove the non-reacted quaternaryammonium salt therefrom. Subsequently, the thus-washed precipitates weredried at 70° C. to obtain a pure-white powder.

20 g of the powder were put in 120 g of ethanol solution containing 10wt. % of hydroxypropyl cellulose and dispersed by roll-milling for 2days to obtain a suspension. To the dispersion, added were 2 g of atri-functional isocyanate (COLONATE HL, trade name—made by NipponPolyurethane Co.) and one g of an ultraviolet absorbent (SEESORB 101S,trade name—made by SHIPRO Chemical Co.), and mixed. The resultingmixture was coated over a lubricant-treated, 6 μm-thick polyethyleneterephthalate film on its lubricant-treated surface, using a wire bar,and dried with a hot air at 120° C. for 5 minutes to form a 5 μm-thicksolid film thereon.

Next, an adhesive composition comprising 2 parts of vinylidenechloride-acrylonitrile copolymer (made by Aldorich Co.) and 20 parts ofMEK was coated on a 100 μm-thick synthetic paper at a wet thickness of50 μm and dried to prepare a base support for a printing paper.

On the adhesive-coated surface of the base support, putted was thepreviously-prepared solid film layer containing the synthetic smectite.Then, this was heated under pressure for heat-welding, by passing itthrough metal rollers heated at 120° C., at a speed of 3 cm/sec. Aftercooled to room temperature, the uppermost, lubricant-treatedpolyethylene terephthalate film was peeled off to obtain a glossy,pure-white printing paper having a dye-receiving layer thereon.

The thus-prepared printing papers were printed by ink jet recording inthe same manner as in Example 2, using the aqueous ink compositions ofGroup (II). As a result, high-quality images composed of true-circulardots were obtained. The thus-printed papers were dipped in water for onefull day. The printed surfaces of the thus-dipped papers were rubbedwith fingers under light pressure, but no dye dissolved out. Thus, thefixation of the dye to the papers was verified to be good. In addition,the solid film containing the intercalated compound did not peel offfrom the base support.

The printed papers were exposed to a Xe light at 90,000 J/m² in theatmosphere at 30° C. and 65% RH. As a result, the percentage of theretention of the dye was 80% or more for each dye. From this, it isnoted that the fastness of the printed images to light is comparable tothat of silver salt photographs.

EXAMPLE 8 Preparation of water-soluble cationic dye-receiving printingpaper for ORP

A solution comprising 2 parts of a polyamide resin (VERSAMID 725, tradename—made by Henckel Hakusui Co.) and 20 parts of a mixed solvent ofMEK/IPA (1/1, by weight) was coated on a 125 μm-thick, transparentpolyethylene terephthalate film having a lubricant layer on its backsurface, at a wet thickness of 100 μm, and then dried to obtain atransparent base support for OHP printing papers.

Next, a dye-receiving layer was formed on the base support in the samemanner as in Example 7 to obtain a transparent, glossy printing paperfor OHP.

The thus-prepared printing papers were printed by ink jet recording inthe same manner as in Example 2, using the aqueous ink compositions ofGroup (I), and transparent, high-quality, natural color images wereobtained.

The thus-printed papers were stored in the atmosphere at 60° C. and 90%RH for 2 weeks, whereupon no dot bled. The fixation of the printedimages was excellent.

COMPARATIVE EXAMPLE 3

Printing papers for OHP were prepared in the same manner as in Example8, except that the synthetic smectite was not used, and these wereprinted by ink jet recording. As a result, the density of the imagesformed herein was about ¼ to ½ of that of the images formed in Example 8for each dye. In addition, the dots were obviously broadened and theimages were blurred. The fixation of the printed images was not good.

EXAMPLE 9 Preparation of water-soluble anionic dye-containing aqueousink compositions

The components shown in Table 4, Table 5 and Table 6 below wereuniformly blended to prepare Group (III) and Group (IV) of aqueous inkcompositions of yellow, magenta and cyan colors for forming colorimages.

In preparing the aqueous ink compositions of Group (IV), a part of thecounter ions of each dye were substituted by organic cations(tetramethylammonium ions) so as to elevate the affinity of the dye fornon-aqueous media to thereby increase the content of the non-aqueousmedium in the composition.

TABLE 4 Group (III) of Aqueous Ink Compositions Component Amount Dye 2parts Yellow C.I. Acid Yellow 23 Magenta C.I. Acid Red 52 Cyan C.l. AcidBlue 9 Glycerin 2 parts Diethylene Glycol 6 parts Water 30 parts

TABLE 5 Group (IV) of Aqueous Ink Compositions Component Amount Dye  2parts Yellow C.I. Acid Yellow 23 Magenta C.I. Acid Red 52 Cyan C.I. AcidBlue 9 Tetramethylammonium Chloride  1 part Diethylene Glycol 20 partsPolyethylene Glycol 20 parts Water 50 parts

TABLE 6 Group (V) of Aqueous Ink Compositions Component Amount Dye 2parts Yellow C.I. Direct Yellow 87 Magenta C.I. Direct Red 227 Cyan C.I.Direct Blue 199 Tetramethylammonium Chloride 1 part Diethylene Glycol 60parts Polyoxyethylene Nonionic Surfactant 0.1 parts Water 30 parts

EXAMPLE 10 Preparation of aqueous anionic dye-receiving printing papers

150 g of synthetic hydrotalcite (DHT-4A, trade name—made by KyowaChemical Industry Co.) were put in one kg of ethanol solution containing10 wt. % of polyvinyl butyral (BL-1, trade name—made by Sekisui ChemicalIndustry Co.) and dispersed with a roll mill for 2 days to obtain asuspension. The suspension was coated on one surface of a 100 μm-thickneutral paper, using a doctor blade, and dried with a hot air at 110° C.for one minute to form a solid film thereon.

Next, a 50 μm-thick polyethylene terephthalate film was covered over thesolid film and heated under pressure for heat-welding, by passing themthrough rollers each having a surface temperature of 120° C. at a speedof one cm/sec. After cooled to room temperature, the uppermostpolyethylene terephthalate film was peeled off to obtain a printingpaper composed of the neutral paper and a transparent and glossy layerformed thereon.

The thus-prepared printing papers were set in a paper-feeding tray in anink jet printer (Desk Jet 505J, trade name—made by Hewlett-Packard,Ltd.) and printed by ink jet recording, using the aqueous inkcompositions of Group (III).

After printing, the printed papers were left as they were for about 5minutes and then subjected to a water-proofness test (fixation test), inwhich their surfaces having images thereon were dipped in water for 24hours to check as to whether or not the dye dissolved out into water. Asa result, no dye dissolved out into water throughout the whole region ofthe printed image ranging from the low-density area to the high-densityarea. Thus, the water-proofness of the printed image was excellent.

COMPARATIVE EXAMPLE 4

Printing papers were prepared in the same manner as in Example 10,except that the synthetic hydrotalcite was not used. These printingpapers were printed by ink jet recording and then subjected to thewater-proofness test, in the same manner as in Example 10. As a result,the dye in the printed images began to dissolve out into waterimmediately after the printed papers were dipped in water, and it almostcompletely dissolved out into water in several hours. In thiscomparative example, the printed images had no fixation.

EXAMPLES 11 TO 14 Preparation of water-soluble anionic dye-receivingprinting papers

100 cc of an aqueous suspension containing 3 g of beaten pulp(RESTIGOUCHE Bleached Pulp HITEE; csf 270 cc) were put in a beakercontaining therein synthetic hydrotalcite (DHT-4C, trade name—made byKyowa Chemical Industry Co.) of the amount indicated in Table 7 below,and the same amount of water was added thereto. Then, while these werelightly stirred with a spoon, 0.06 g (12.0% as its solid content) of asizing agent (MACOPELU 12, trade name—made by Dick Hercules Co.) toprevent the paper from shrinking in the presence of water and 0.12 g ofa fixing agent (KAIMEN 557-7, trade name—made by Dick Hercules Co.) toaccelerate pulp-to-pulp adhesion or pulp-to-pigment adhesion were addedthereto. The resulting mixture was ground in a mixer for about 2minutes, then put in a water tank in a paper-making machine, and thedispersion in the tank was stirred within a mesh-like stirrer.

Next, water was drawn out of the water tank all at a time, and awater-absorbing paper was put over the sheet-like substance deposited atthe bottom of the water tank and pressed with a heavy stone roller.Next, the water-absorbing paper was removed, and the raw paper formed atthe bottom of the tank was peeled off from the lowermost screen mesh anddewatered in a drier at 160° C. to obtain a printing paper composed ofintegrated dye-receiving layer and support.

TABLE 7 Amount of Synthetic Hydrotalcite Added Example No. Amount Added(g) 11 4.2 12 3.3 13 1.0 14 0.5

The thus-obtained printing papers were printed by ink jet recording inthe same manner as in Example 10, using the aqueous ink compositions ofGroup (IV) having a higher content of the non-aqueous medium than theaqueous ink compositions of Group (III). The formed dots bled a little,being different from those formed in Example 10, but the bleeding of thedots does not cause any problem in practical use. The penetration of theaqueous ink compositions into the printing papers was good.

Next, the thus-printed papers were subjected to a solvent resistancetest (using ethanol), in which the papers were dipped in ethanol tocheck as to whether or not the dye dissolved out into ethanol. As aresult, substantially no dye dissolved out from the printed papers ofExamples 11 to 13 at every density of the printed images, and theprinted images had excellent solvent resistance (fixation). In theprinted papers of Example 14, the dye dissolved out only slightly fromthe high-density area in the formed images, which, however, causes noproblem in practical use. From these results, it is noted that thesolvent resistance (alcohol resistance) of the printing papers of theseexamples was greatly improved due to the incorporation of theintercalated compound thereinto.

COMPARATIVE EXAMPLE 5

Printing papers were prepared in the same manner as in Examples 11 to14, except that the synthetic hydrotalcite was not used. These printingpapers were printed by ink jet recording and subjected to the solventresistance test for the printed images, in the same manner as inExamples 11 to 14. As a result, the printed dye immediately dissolvedout from all the image regions having various densities. Thus, thesolvent resistance of the printing papers in this comparative examplewas not good.

EXAMPLE 14 Preparation of water-soluble anionic dye-receiving printingpapers

20 g of synthetic hydrotalcite (DHT-4C, trade name —made by KyowaChemical Industry Co.) were dispersed and swollen in one liter of water,and ethanol of the same amount was added to the dispersion. Whilestirring, sodium decanoate (2 mg equivalents) dissolved in 200 cc ofethanol was dropwise added to the dispersion. This was allowed to standat room temperature for one day, whereupon granular aggregatesprecipitated. The precipitates were separated from the dispersion byfiltration and washed with ethanol to remove the non-reacted fatty acidsalt therefrom. Subsequently, the thus-washed precipitates were dried at70° C. to obtain a pure-white powder.

20 g of the powder were put in 120 g of ethanol solution containing 10wt. % of hydroxypropyl cellulose and dispersed by roll-milling for 2days to obtain a suspension. To the dispersion, added were 2 g of atri-functional isocyanate (COLONATE HL, trade name—made by NipponPolyurethane Co.) and one g of an ultraviolet absorbent (SEESORB 101S,trade name—made by SHIPRO Chemical Co.), and mixed. The resultingmixture was coated over a lubricant-treated, 6 μm-thick polyethyleneterephthalate film on its lubricant-treated surface, using a wire bar,and dried with a hot air at 120° C. for 5 minutes to form a 5 μm-thicksolid film thereon.

Next, an adhesive composition comprising 2 parts of vinylidenechloride-acrylonitrile copolymer (made by Aldorich Co.) and 20 parts ofMEK was coated on a 100 μm-thick synthetic paper at a wet thickness of50 μm and dried to prepare a base support for a printing paper.

On the adhesive-coated surface of the base support, putted was thepreviously-prepared solid film layer containing the synthetichydrotalcite. Then, this was heated under pressure for heat-welding, bypassing it through metal rollers heated at 120° C., at a speed of 3cm/sec. After cooled to room temperature, the uppermost,lubricant-treated polyethylene terephthalate film was peeled off toobtain a glossy, pure-white printing paper having a dye-receiving layerthereon.

The thus-prepared printing papers were printed by ink jet recording inthe same manner as in Examples 11 to 14, using the aqueous inkcompositions of Group (IV). As a result, high-quality images composed oftrue-circular dots were obtained.

The thus-printed papers were dipped in water for one full day. Theprinted surfaces of the thus-dipped papers were rubbed with fingersunder light pressure, but no dye dissolved out. Thus, the fixation ofthe dye to the papers was verified to be good. In addition, the solidfilm containing the intercalated compound did not peel off from the basesupport.

EXAMPLE 16 Preparation of water-soluble anionic dye-receiving printingpaper for ORP

A solution comprising 2 parts of a polyamide resin (VERSAMID 725, tradename—made by Henckel Hakusui Co.) and 20 parts of a mixed solvent ofMEK/IPA (1/1, by weight) was coated on a 125 μm-thick, transparentpolyethylene terephthalate film having a lubricant layer on its backsurface, at a wet thickness of 100 μm, and then dried to obtain atransparent base support for OHP printing papers.

Next, a dye-receiving layer was formed on the base support in the samemanner as in Example 15 to obtain a transparent, glossy printing paperfor OHP.

The thus-prepared printing papers were printed by ink jet recording inthe same manner as in Example 11 to 14, using the aqueous inkcompositions of Group (III), and transparent, high-quality, naturalcolor images were obtained.

The thus-printed papers were stored in the atmosphere at 60° C. and 90%RH for 2 weeks, whereupon no dot bled. The fixation of the printedimages was excellent.

COMPARATIVE EXAMPLE 6

Printing papers for OHP were prepared in the same manner as in Example16, except that the synthetic hydrotalcite was not used, and these wereprinted by ink jet recording. As a result, the density of the imagesformed herein was about ¼ to ½ of that of the images formed in Example16 for each dye. In addition, the dots were obviously broadened and theimages were blurred. The fixation of the printed images was not good.

EXAMPLE 17

This example is to demonstrate the preparation of water-soluble cationicdye-receiving printing papers, in which a composition for forming awater-soluble cationic dye-receiving layer was jetted out ontocommercial regenerated papers through ink jet nozzles and dried thereon.

First, 150 g of synthetic hectorite (LAPONITE, trade name—made by NipponSilica Industrial Co.) were put in one kg of isopropanol solutioncontaining 1 wt. % of polyvinyl butyral (BL-1, trade name—made bySekisui Chemical Industry Co.) and 1 wt. % of propylene glycol anddispersed with a roll mill for 2 days to obtain a suspension containingparticles of the synthetic hectorite having a particle size of 1 μm orless.

The suspension was substituted for the content in the cartridge for anink jet printer (Desk Jet HP51626A, trade name—made by Hewlett-PackardLtd.), and the cartridge was set in an ink jet printer (505J, trade name—made by Hewlett-Packard Ltd.). Using this, A4-size, commercialregenerated papers were solidwise printed and dried to obtain printingpapers having an increased whiteness.

The thus-prepared printing papers were set in a paper-feeding tray in anink jet printer (Desk Jet 505J, trade name—made by Hewlett-Packard,Ltd.), while one of the water-soluble ink compositions of Group (I) wassubstituted for the content in the cartridge for the ink jet printer(Desk Jet HP51626A, trade name—made by Hewlett-Packard Ltd.), and thesewere printed by ink jet recording using the substituted cartridge. Ofthe water-soluble ink compositions of Group (I), the black inkcomposition was not used.

After printing, the printed papers were left as they were for about 5minutes and then subjected to a water-proofness test (fixation test), inwhich their surfaces having images thereon were dipped in distilledwater for one full day to check as to whether or not the dye dissolvedout into water. As a result, no dye dissolved out into water throughoutthe whole region of the printed image ranging from the low-density areato the high-density area. Thus, the water-proofness of the printed imagewas excellent.

COMPARATIVE EXAMPLE 7

Printing papers were prepared in the same manner as in Example 17,except that the synthetic hectorite was not used. These printing paperswere printed by ink jet recording and then subjected to thewater-proofness test, in the same manner as in Example 17. As a result,the dye in the printed images began to dissolve out into waterimmediately after the printed papers were dipped in water, and it almostcompletely dissolved out into water in several ten minutes. In thiscomparative example, the printed images had no fixation.

EXAMPLE 18 Preparation of water-soluble cationic dye-receiving printingpapers

This example is to demonstrate the preparation of water-soluble cationicdye-receiving printing papers, in which a composition for forming awater-soluble cationic dye-receiving layer was jetted out ontocommercial regenerated papers through jetting nozzles and dried thereon.

First, 20 g of synthetic smectite (SWN, trade name —made by CorpChemical Co.) were dispersed and swollen in one liter of water, andethanol of the same amount was added to the dispersion. While stirring,0.22 g (0.33 mg equivalents) of tetra-n-decylammonium bromide dissolvedin 200 cc of ethanol were dropwise added to the dispersion. This wasallowed to stand at room temperature for one day, whereupon granularaggregates precipitated. The precipitates were separated from thedispersion by filtration and washed with ethanol to remove thenon-reacted quaternary ammonium salt therefrom. Subsequently, thethus-washed precipitates were dried at 70° C. to obtain a pure-whitepowder.

12 g of the powder were put in 120 g of ethanol/toluene mixturecontaining 1 wt. % of polyamide and dispersed by sand-milling until thedispersed smectite particles might have a particle size in the order ofsub-microns. In this way, a suspension was obtained. To the dispersion,added were 3 g of ethylene carbonate and 0.03 g of an ultravioletabsorbent (SEESORB 101S, trade name—made by SHIPRO Chemical Co.), andmixed. The resulting mixture was filled in the jetting head 50 in aserial-type ink jet recording device such as that shown in FIG. 4, whileone of the aqueous ink compositions of Group (II) was filled in theprinting head 41 in the same. Using the device, 115 μm-thick PET filmsfor OHP were printed to obtain full-color prints thereon. As a result,high-quality images composed of true-circular dots were obtained. Thetransparency of the printed films were sufficient for practical use.

A commercial antistatic spray consisting essentially of ethanol wasexcessively sprayed over the thus-printed films, but the printed imagesdid not bleed and their fixation was excellent.

COMPARATIVE EXAMPLE 8

Color images were obtained in the same manner as in Example 18, exceptthat the synthetic smectite was not used. As a result, since thepenetrability of the ink was poor, the dots forming the pale color areasin the images had irregular shapes. In addition, a part of the ink wasnot absorbed by the dye-receiving layer but remained thereon in the deepcolor areas in the images with the result that the images became blurredwhen their surfaces were rubbed with fingers.

When a commercial anti-static spray consisting essentially of ethanolwas sprayed over the printed films were, then the images also becameblurred.

EXAMPLE 19

This example is to demonstrate the preparation of water-soluble anionicdye-receiving postcards, in which a composition for forming awater-soluble anionic dye-receiving layer was sprayed over commercialregenerated papers using a commercial air brush and dried thereon.

150 g of synthetic hydrotalcite (DHT-4A, trade name—made by KyowaChemical Industry Co.) and 300 g of polypropylene glycol were put in onekg of ethanol solution containing 1.5 wt. % of polyvinyl butyral (BL-S,trade name—made by Sekisui Chemical Industry Co.) and dispersed byroll-milling for 2 weeks until the dispersed hydrotalcite particlesmight have a particle size in the order of sub-microns. Thus, asuspension of the synthetic hydrotalcite was obtained.

The thus-obtained suspension was filled in the solution tank of acommercial air brush and sprayed over the entire back surfaces ofpostcards having excellent dot-reproducibility in an amount of 5cc/postcard. After left as they were for one minute at room temperature,water-soluble anionic dye-receiving postcards were obtained.

The thus-obtained dye-receiving postcards were printed on theirdye-receiving surfaces by ink jet recording, using an ink jet printer(1200C, trade name—made by Hewlett-Packard, Ltd.), and sharp images withexcellent dot-reproducibility were obtained.

The thus-printed postcards were stored in the atmosphere at 60° C. and90% RH for 2 weeks, whereupon no dots bled though the images somewhatfaded.

COMPARATIVE EXAMPLE 9

Color images were obtained by the same ink jet recording as in Example19, except that the synthetic smectite was not used. The printedpostcards were stored in the atmosphere at 60° C. and 90% RH for 2weeks, whereupon the images became blurred and faded.

EXAMPLE 20

This example is to demonstrate the preparation of water-soluble anionicdye-receiving printing papers, in which a composition for forming awater-soluble anionic dye-receiving layer was jetted out onto commercialregenerated papers through jetting nozzles and dried thereon.

20 g of synthetic hydrotalcite (DHT-4C, trade name —made by KyowaChemical Industry Co.) were dispersed and swollen in one liter of water,and ethanol of the same amount was added to the dispersion. Whilestirring, sodium decanoate (2 mg equivalents) dissolved in 200 cc ofethanol was dropwise added to the dispersion. This was allowed to standat room temperature for one day, whereupon granular aggregatesprecipitated. The precipitates were separated from the dispersion byfiltration and washed with ethanol to remove the non-reacted fatty acidsalt therefrom. Subsequently, the thus-washed precipitates were dried at70° C. to obtain a pure-white powder of decanoate-treated hydrotalcite.

Next, 2 parts of the decanoate-treated hydrotalcite powder, 1 part ofhydroxypropyl cellulose, 4 parts of vinyl pyrrolidone-vinyl acetatecopolymer, 1 part of titanium oxide, 1 part of polyethylene glycol and18 parts of ethanol were dispersed by roll-milling for 3 weeks to obtaina suspension containing decanoate-treated hydrotalcite particles havinga mean particle size of 0.3 μm.

The thus-obtained suspension was filled in the jetting head of aserial-type ink jet recording device of the same type as that employedin Example 18, while one of the aqueous ink compositions of Group (V)was filled in its printing head. First, the suspension was jetted outonto the label surfaces (on which sound signals are not recorded) ofcompact discs (CDs) through the jetting head while imagewise scanningthem to thereby form a white dye-receiving layer thereon, andimmediately after the formation, an image was printed on the layer inaccordance with a video image signal.

The thus-printed CDs were left as they were for several minutes, andthen a commercial lacquer spray containing a large amount of an organicsolvent was sprayed over the entire image formed so as to make the imageglossy and resistant to abrasion, whereupon the image was neitherblurred nor bled.

COMPARATIVE EXAMPLE 10

Color images were obtained by the same ink jet recording as in Example20, except that the synthetic hydrotalcite was not used. The samelacquer spray as that used in Example 20 was sprayed over thethus-printed CDs, whereupon the image was blurred and bled.

According to the present invention, images comparable to those by silversalt photography may be formed with excellent fixation and highresolution by ink jet recording. In particular, when transparentintercalated compounds and binder resins are used in the presentinvention, images with high saturation may be obtained.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A composition for forming a dye-receiving layercomprising from about greater than 40 to about less than 70% by weightbased on solids of an intercalated compound that fixes water-solubledyes to the dye-receiving layer due to intercalation based on anion-exchange between the intercalated compound and the water-solubledyes, said intercalated compound having a plurality of intercalatedcompound particles which are dispersed so as to form a mean grain sizeof 1 μm or less for each of said intercalated compound particles; fromabout 2 to about 50% by weight based on solids of a binder resin; and asolvent.
 2. The composition for forming a dye-receiving layer as claimedin claim 1, in which said intercalated compound is a layered inorganicpolymer having exchangeable cations.
 3. The composition for forming adye-receiving layer as claimed in claim 2, in which said layeredinorganic polymer having exchangeable cations is chosen from amongmontmorillonoids.
 4. The composition for forming a dye-receiving layeras claimed in claim 3, in which said montmorillonoids are represented bya formula (1): (X,Y)_(2˜3)Z₄O₁₀(OH)₂.mH₂O.(W_(⅓))   (1) wherein Xrepresents Al, Fe(III), Mn(III) or Co(III); Y represents Mg, Fe(II), Ni,Zn or Li; Z represents Si or Al; W represents K, Na or Ca; H₂O is anintercalated water; and m represents an integer.
 5. The composition forforming a dye-receiving layer as claimed in claim 5, wherein saidintercalated compound is selected from the group consisting ofcation-exchangeable and anion-exchangeable intercalated compounds. 6.The composition for forming a dye-receiving layer as claimed in claim 1,in which said intercalated compound is a layered inorganic polymerhaving exchangeable anions.
 7. The composition for forming adye-receiving layer as claimed in claim 6, in which said layeredinorganic polymer having exchangeable anions is chosen from amonghydrotalcite-group minerals.
 8. The composition for forming adye-receiving layer as claimed in claim 7, in which saidhydrotalcite-group mineral is natural hydrotalcite of a formula (2):Mg₆Al₂(OH)₁₆.CO₃.4H₂O   (2).
 9. The composition for forming adye-receiving layer as claimed in claim 1, which contains saidintercalated compound in an amount of from 10 to 90% by weight relativeto the solid content in the composition.
 10. The composition for forminga dye-receiving layer as claimed in claim 1, in which said binder resinis a hydrophilic resin.
 11. The composition for forming a dye-receivinglayer as claimed in claim 10, in which said binder resin is chosen fromamong polyvinyl butyral resins, hydroxypropyl cellulose resins, vinylpyrrolidone-vinyl acetate copolymer resins, polyvinyl alcohol resins andpolyvinyl acetal resins.
 12. The composition for forming a dye-receivinglayer as claimed in claim 1, in which said solvent is a lower alcohol.13. The composition for forming a dye-receiving layer as claimed inclaim 1, which comprises from 20 to 60% by weight of said solvent. 14.The composition for forming a dye-receiving layer as claimed in claim 1,in which each of said intercalated compound particles has a mean grainsize that ranges from 0.01 μm to 0.5 μm.
 15. A composition for forming adye-receiving layer consisting essentially of from about greater than 40to about less than 70% by weight based on solids of an intercalatedcompound that fixes water-soluble dyes to the dye-receiving layer due toan intercalation based on an ion-exchange between the intercalatedcompound and the water-soluble dyes, said intercalated compound having aplurality of intercalated compound particles which are dispersed so asto form a mean grain size of 1 μm or less for each of said intercalatedcompound particles; from about 2 to about 50% by weight based on solidsof a binder resin; and a solvent.
 16. A composition for forming a dyereceiving layer comprising from about greater than 40 to about less than70% by weight based on solids of an intercalated compound that fixeswater-soluble dyes to the dye-receiving layer due to intercalation basedon an ion-exchange between the intercalated compound and thewater-soluble dyes, said intercalated compound being pre-reacted with anorganic ion so that at least some of the organic ions are introducedinto the intercalated compound, said intercalated compound having aplurality of intercalated compound particles which are dispersed so asto form a mean grain size of 1 μm or less for each of said intercalatedcompound particles; from about 2 to about 50% by weight based on solidsof a binder resin; and a solvent.